3,6-Dimethyl-1-phenyl-4-(2-thien­yl)-8-(2-thienylmethyl­ene)-5,6,7,8-tetra­hydro-1H-pyrazolo[3,4-b][1,6]naphthyridine

Peng, J.; Han, Z.; Ma, N.; Tu, S.

doi:10.1107/S1600536809014810

organic compounds

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ISSN: 2056-9890

Volume 65| Part 5| May 2009| Pages o1109-o1110

doi:10.1107/S1600536809014810

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3,6-Dimethyl-1-phenyl-4-(2-thienyl)-8-(2-thienylmethylene)-5,6,7,8-tetrahydro-1H-pyrazolo[3,4-b][1,6]naphthyridine

Juhua Peng,^a Zhengguo Han,^b Ning Ma ^b and Shujiang Tu ^b ^*

^aLianyungang Teachers' College, Lianyungang 222006, People's Republic of China, and ^bCollege of Chemistry and Chemical Engineering, Xuzhou Normal University, Xuzhou 221116, People's Republic of China
^*Correspondence e-mail: laotu2001@263.net

(Received 18 April 2009; accepted 21 April 2009; online 25 April 2009)

In the molecule of the title compound, C₂₆H₂₂N₄S₂, the pyrazole ring is oriented at a dihedral angle of 0.85 (3)° with respect to the adjacent naphthyridine ring, while the other ring of naphthyridine adopts an envelope conformation. The dihedral angle between phenyl and pyrazole rings is 87.65 (3)°. In the crystal structure, weak intermolecular C—H⋯N interactions link the molecules into chains. The π–π contacts between the naphthyridine rings and the naphthyridine and thiophene rings [centroid–centroid distances = 3.766 (3) and 3.878 (3) Å] may further stabilize the structure. A weak C—H⋯π interaction is also present.

Related literature

For the biological activity of naphthyridines, see: Abou et al. (2001 ); Aleem et al. (2002 ); Blagg et al. (2003 ); Ohta et al. (2004 ). For the biological properties of pyrazolopyridine derivatives, see: Lynck et al. (1988 ); Fucini et al. (2008 ); Warshakoon et al. (2006 ). They are also active against gram positive and gram negative bacteria, see: El-Dean et al. (1991 ) and inhibit cholesterol formation, see: Fujikawa et al. (1989 , 1990 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₂₆H₂₂N₄S₂
M_r = 454.60
Triclinic, $[P \overline 1]$
a = 10.7187 (16) Å
b = 10.9704 (19) Å
c = 11.153 (2) Å
α = 109.785 (2)°
β = 102.364 (1)°
γ = 104.201 (1)°
V = 1131.0 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 298 K
0.18 × 0.17 × 0.16 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.955, T_max = 0.960
5846 measured reflections
3918 independent reflections
2322 reflections with I > 2σ(I)
R_int = 0.025

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.176
S = 1.00
3918 reflections
291 parameters
H-atom parameters constrained
Δρ_max = 0.31 e Å⁻³
Δρ_min = −0.43 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C26—H26⋯N2ⁱ	0.93	2.57	3.445 (3)	157
C20—H20⋯Cg6ⁱⁱ	0.93	2.93	3.680 (3)	139
Symmetry codes: (i) x+1, y+1, z; (ii) x+1, y+1, z+1. Cg6 is the centroid of the S1/C23–C26 ring.

Data collection: SMART (Bruker, 1998 ); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809014810/hk2672sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809014810/hk2672Isup2.hkl

checkCIF report

Comment top

Naphthyridines have received considerable attention over the past years because of their wide range of biological activities including antitumor (Abou et al., 2001; Aleem et al., 2002), anti-inflammatory (Blagg et al., 2003) and antifungal (Ohta et al., 2004) activities. Pyrazolopyridine derivatives are important heterocyclic compounds, which exhibit a diverse range of biological properties such as new inhibitors of xanthine oxidases (Lynck et al., 1988), as Polo-like kinase 1 inhibitors (Fucini et al., 2008) and HIF-1alpha prolyl hydroxylase inhibitors (Warshakoon et al., 2006). They also have proven to be active against gram positive and gram negative bacterias (El-Dean et al., 1991) and also as compounds for the inhibition of cholesterol formation (Fujikawa et al., 1989, 1990). We report herein the crystal structure of the title compound, containing the skeletons of naphthyridine and pyrazolopyridine.

In the molecule of the title compound (Fig. 1), the bond lengths (Allen et al., 1987) and angles are within normal ranges. Rings A (N1/N2/C1-C3), B (N3/C2-C4/C6/C7), D (C10-C15), E (S2/C17-C20) and F (S1/C23-C26) are, of course, planar, and they are oriented at dihedral angles of A/B = 0.85 (3), A/D = 87.65 (3) and B/E = 18.10 (4) °. Ring C (N4/C5-C9) adopts envelope conformation, with atom N4 displaced by 0.660 (3) Å from the plane of the other ring atoms.

In the crystal structure, weak intermolecular C-H···N interactions (Table 1) link the molecules into chains (Fig. 2), in which they may be effective in the stabilization of the structure. The π–π contacts between the naphthyridine rings and the naphthyridine and thiophene rings, Cg2—Cg2ⁱ and Cg2—Cg6ⁱⁱ [symmetry codes: (i) 1 - x, 1 - y, 1 - z, (ii) -x, 1 - y, 1 - z, where Cg2 and Cg6 are centroids of the rings B (N3/C2-C4/C6/C7) and F (S1/C23-C26), respectively] may further stabilize the structure, with centroid-centroid distances of 3.766 (3) and 3.878 (3) Å, respectively. There also exists a weak C-H···π interaction (Table 1).

Related literature top

For the biological activity of naphthyridines, see: Abou et al. (2001); Aleem et al. (2002); Blagg et al. (2003); Ohta et al. (2004). For the biological properties of pyrazolopyridine derivatives, see: Lynck et al. (1988); Fucini et al. (2008); Warshakoon et al. (2006). They are also active against gram positive and gram negative bacteria, see: El-Dean et al. (1991) and inhibit cholesterol formation, see: Fujikawa et al. (1989, 1990). For bond-length data, see: Allen et al. (1987). Cg6 is the centroid of the S1/C23–C26 ring.

Experimental top

The title compound was prepared by the reaction of of 1-methyl-3,5-bis(thiophen -2-ylmethylene)piperidin-4-one (1 mmol) and 3-methyl-1-phenyl-1H-pyrazol -5- amine (1 mmol) in glycol (2 ml).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. A partial packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.

3,6-Dimethyl-1-phenyl-4-(2-thienyl)-8-(2-thienylmethylene)-5,6,7,8-tetrahydro- 1H-pyrazolo[3,4-b][1,6]naphthyridine top

Crystal data top

C₂₆H₂₂N₄S₂	Z = 2
M_r = 454.60	F(000) = 476
Triclinic, P1	D_x = 1.335 Mg m⁻³
Hall symbol: -P 1	Melting point = 452–453 K
a = 10.7187 (16) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.9704 (19) Å	Cell parameters from 1616 reflections
c = 11.153 (2) Å	θ = 2.3–24.8°
α = 109.785 (2)°	µ = 0.26 mm⁻¹
β = 102.364 (1)°	T = 298 K
γ = 104.201 (1)°	Block, yellow
V = 1131.0 (3) Å³	0.18 × 0.17 × 0.16 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3918 independent reflections
Radiation source: fine-focus sealed tube	2322 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.025
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −12→11
T_min = 0.955, T_max = 0.960	k = −12→13
5846 measured reflections	l = −13→13

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.176	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0957P)²] where P = (F_o² + 2F_c²)/3
3918 reflections	(Δ/σ)_max < 0.001
291 parameters	Δρ_max = 0.31 e Å⁻³
0 restraints	Δρ_min = −0.43 e Å⁻³

Crystal data top

C₂₆H₂₂N₄S₂	γ = 104.201 (1)°
M_r = 454.60	V = 1131.0 (3) Å³
Triclinic, P1	Z = 2
a = 10.7187 (16) Å	Mo Kα radiation
b = 10.9704 (19) Å	µ = 0.26 mm⁻¹
c = 11.153 (2) Å	T = 298 K
α = 109.785 (2)°	0.18 × 0.17 × 0.16 mm
β = 102.364 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3918 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2322 reflections with I > 2σ(I)
T_min = 0.955, T_max = 0.960	R_int = 0.025
5846 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.176	H-atom parameters constrained
S = 1.00	Δρ_max = 0.31 e Å⁻³
3918 reflections	Δρ_min = −0.43 e Å⁻³
291 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
S1	1.09086 (12)	0.85725 (11)	1.54317 (11)	0.0768 (4)
S2	0.32900 (12)	0.10633 (12)	1.04051 (11)	0.0826 (4)
N1	0.5616 (3)	0.2524 (3)	1.5917 (3)	0.0481 (7)
N2	0.4340 (3)	0.1519 (3)	1.5362 (3)	0.0529 (8)
N3	0.6907 (3)	0.4256 (3)	1.5345 (3)	0.0442 (7)
N4	0.7120 (3)	0.5378 (3)	1.2194 (3)	0.0507 (7)
C1	0.3741 (3)	0.1548 (3)	1.4219 (3)	0.0477 (9)
C2	0.4614 (3)	0.2600 (3)	1.3994 (3)	0.0432 (8)
C3	0.5805 (3)	0.3207 (3)	1.5104 (3)	0.0417 (8)
C4	0.4568 (3)	0.3106 (3)	1.2988 (3)	0.0416 (8)
C5	0.5739 (3)	0.4802 (4)	1.2173 (3)	0.0518 (9)
H5A	0.5198	0.4087	1.1282	0.062*
H5B	0.5338	0.5520	1.2358	0.062*
C6	0.5706 (3)	0.4201 (3)	1.3199 (3)	0.0432 (8)
C7	0.6845 (3)	0.4735 (3)	1.4386 (3)	0.0417 (8)
C8	0.8071 (3)	0.5867 (3)	1.4584 (3)	0.0435 (8)
C9	0.7958 (4)	0.6439 (4)	1.3528 (4)	0.0565 (10)
H9A	0.7567	0.7160	1.3767	0.068*
H9B	0.8861	0.6849	1.3509	0.068*
C10	0.6506 (3)	0.2705 (3)	1.7162 (3)	0.0458 (8)
C11	0.5969 (4)	0.2282 (4)	1.8042 (4)	0.0588 (10)
H11	0.5032	0.1886	1.7824	0.071*
C12	0.6838 (4)	0.2456 (4)	1.9247 (4)	0.0659 (11)
H12	0.6477	0.2174	1.9836	0.079*
C13	0.8214 (4)	0.3032 (4)	1.9589 (4)	0.0690 (11)
H13	0.8788	0.3151	2.0405	0.083*
C14	0.8741 (4)	0.3437 (4)	1.8704 (4)	0.0643 (11)
H14	0.9679	0.3820	1.8923	0.077*
C15	0.7896 (4)	0.3281 (4)	1.7496 (4)	0.0555 (10)
H15	0.8265	0.3564	1.6911	0.067*
C16	0.2334 (4)	0.0573 (4)	1.3364 (4)	0.0625 (11)
H16A	0.2020	−0.0031	1.3773	0.094*
H16B	0.2341	0.0036	1.2485	0.094*
H16C	0.1737	0.1087	1.3284	0.094*
C17	0.3367 (3)	0.2461 (3)	1.1741 (3)	0.0459 (8)
C18	0.2173 (3)	0.2811 (4)	1.1483 (3)	0.0498 (9)
H18	0.2016	0.3556	1.2057	0.060*
C19	0.1251 (4)	0.1809 (5)	1.0180 (4)	0.0675 (11)
H19	0.0395	0.1832	0.9821	0.081*
C20	0.1702 (4)	0.0850 (4)	0.9523 (4)	0.0657 (11)
H20	0.1202	0.0143	0.8675	0.079*
C21	0.7112 (4)	0.5941 (4)	1.1182 (4)	0.0688 (11)
H21A	0.6811	0.6719	1.1425	0.103*
H21B	0.6506	0.5245	1.0320	0.103*
H21C	0.8015	0.6230	1.1136	0.103*
C22	0.9196 (3)	0.6288 (3)	1.5629 (3)	0.0482 (9)
H22	0.9119	0.5826	1.6186	0.058*
C23	1.0514 (4)	0.7338 (3)	1.6046 (3)	0.0480 (9)
C24	1.1687 (3)	0.7475 (3)	1.7027 (3)	0.0425 (8)
H24	1.1705	0.6932	1.7511	0.051*
C25	1.2830 (4)	0.8555 (4)	1.7167 (4)	0.0665 (11)
H25	1.3696	0.8787	1.7750	0.080*
C26	1.2548 (4)	0.9214 (4)	1.6380 (4)	0.0740 (13)
H26	1.3193	0.9945	1.6364	0.089*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0715 (8)	0.0687 (7)	0.0740 (8)	−0.0057 (6)	0.0132 (6)	0.0382 (6)
S2	0.0723 (8)	0.0782 (8)	0.0661 (7)	0.0296 (6)	0.0035 (6)	0.0026 (6)
N1	0.0430 (17)	0.0511 (17)	0.0446 (16)	0.0028 (14)	0.0117 (14)	0.0245 (14)
N2	0.0424 (17)	0.0533 (18)	0.0526 (18)	−0.0015 (14)	0.0116 (14)	0.0248 (15)
N3	0.0400 (16)	0.0432 (15)	0.0403 (15)	0.0046 (13)	0.0104 (13)	0.0154 (13)
N4	0.0521 (18)	0.0571 (17)	0.0439 (16)	0.0121 (15)	0.0142 (14)	0.0278 (15)
C1	0.042 (2)	0.047 (2)	0.048 (2)	0.0066 (16)	0.0138 (16)	0.0192 (17)
C2	0.0382 (19)	0.0431 (18)	0.0415 (18)	0.0080 (15)	0.0127 (15)	0.0140 (15)
C3	0.0405 (19)	0.0447 (18)	0.0362 (18)	0.0095 (16)	0.0102 (15)	0.0177 (15)
C4	0.0378 (19)	0.0428 (18)	0.0402 (18)	0.0126 (15)	0.0104 (15)	0.0147 (15)
C5	0.049 (2)	0.057 (2)	0.051 (2)	0.0140 (18)	0.0126 (17)	0.0300 (18)
C6	0.042 (2)	0.0457 (19)	0.0436 (19)	0.0134 (16)	0.0157 (16)	0.0204 (16)
C7	0.0414 (19)	0.0432 (18)	0.0415 (19)	0.0128 (16)	0.0150 (16)	0.0192 (16)
C8	0.046 (2)	0.0409 (18)	0.0402 (18)	0.0103 (16)	0.0160 (16)	0.0157 (15)
C9	0.056 (2)	0.056 (2)	0.057 (2)	0.0079 (19)	0.0181 (19)	0.0306 (19)
C10	0.047 (2)	0.0435 (19)	0.045 (2)	0.0110 (16)	0.0141 (17)	0.0204 (16)
C11	0.055 (2)	0.065 (2)	0.054 (2)	0.0109 (19)	0.0169 (19)	0.029 (2)
C12	0.075 (3)	0.080 (3)	0.054 (2)	0.025 (2)	0.026 (2)	0.040 (2)
C13	0.070 (3)	0.086 (3)	0.052 (2)	0.029 (2)	0.012 (2)	0.033 (2)
C14	0.050 (2)	0.072 (3)	0.063 (3)	0.017 (2)	0.008 (2)	0.027 (2)
C15	0.055 (2)	0.062 (2)	0.053 (2)	0.0169 (19)	0.0186 (19)	0.0284 (19)
C16	0.048 (2)	0.061 (2)	0.063 (2)	−0.0026 (19)	0.0112 (19)	0.027 (2)
C17	0.044 (2)	0.0469 (19)	0.0428 (19)	0.0086 (16)	0.0146 (16)	0.0186 (16)
C18	0.041 (2)	0.058 (2)	0.0372 (18)	0.0101 (17)	0.0098 (16)	0.0105 (17)
C19	0.047 (2)	0.089 (3)	0.072 (3)	0.026 (2)	0.014 (2)	0.043 (3)
C20	0.055 (2)	0.061 (2)	0.049 (2)	0.001 (2)	−0.0019 (19)	0.0084 (19)
C21	0.072 (3)	0.083 (3)	0.059 (2)	0.018 (2)	0.021 (2)	0.045 (2)
C22	0.051 (2)	0.0463 (19)	0.047 (2)	0.0076 (17)	0.0196 (18)	0.0229 (17)
C23	0.051 (2)	0.0436 (19)	0.0426 (19)	0.0065 (17)	0.0194 (17)	0.0146 (16)
C24	0.0415 (19)	0.0375 (17)	0.0444 (19)	0.0098 (15)	0.0167 (16)	0.0132 (15)
C25	0.047 (2)	0.072 (3)	0.061 (2)	0.011 (2)	0.017 (2)	0.011 (2)
C26	0.064 (3)	0.060 (2)	0.068 (3)	−0.014 (2)	0.025 (2)	0.016 (2)

Geometric parameters (Å, º) top

S1—C26	1.672 (5)	C11—C12	1.384 (5)
S1—C23	1.718 (4)	C11—H11	0.9300
S2—C20	1.689 (4)	C12—C13	1.363 (5)
S2—C17	1.708 (3)	C12—H12	0.9300
N1—C3	1.375 (4)	C13—C14	1.379 (6)
N1—N2	1.381 (3)	C13—H13	0.9300
N1—C10	1.424 (4)	C14—C15	1.381 (5)
N2—C1	1.314 (4)	C14—H14	0.9300
N3—C3	1.334 (4)	C15—H15	0.9300
N3—C7	1.338 (4)	C16—H16A	0.9600
N4—C5	1.451 (4)	C16—H16B	0.9600
N4—C9	1.455 (4)	C16—H16C	0.9600
N4—C21	1.458 (4)	C17—C18	1.423 (5)
C1—C2	1.428 (4)	C18—C19	1.438 (5)
C1—C16	1.493 (5)	C18—H18	0.9300
C2—C3	1.398 (4)	C19—C20	1.325 (5)
C2—C4	1.407 (4)	C19—H19	0.9300
C4—C6	1.398 (4)	C20—H20	0.9300
C4—C17	1.487 (4)	C21—H21A	0.9600
C5—C6	1.504 (5)	C21—H21B	0.9600
C5—H5A	0.9700	C21—H21C	0.9600
C5—H5B	0.9700	C22—C23	1.448 (4)
C6—C7	1.420 (4)	C22—H22	0.9300
C7—C8	1.486 (4)	C23—C24	1.417 (5)
C8—C22	1.336 (5)	C24—C25	1.417 (5)
C8—C9	1.508 (5)	C24—H24	0.9300
C9—H9A	0.9700	C25—C26	1.344 (6)
C9—H9B	0.9700	C25—H25	0.9300
C10—C15	1.379 (5)	C26—H26	0.9300
C10—C11	1.389 (5)

C26—S1—C23	93.1 (2)	C13—C12—H12	119.3
C20—S2—C17	92.60 (19)	C11—C12—H12	119.3
C3—N1—N2	110.2 (3)	C12—C13—C14	118.9 (4)
C3—N1—C10	130.4 (3)	C12—C13—H13	120.5
N2—N1—C10	119.4 (3)	C14—C13—H13	120.5
C1—N2—N1	107.4 (3)	C13—C14—C15	121.0 (4)
C3—N3—C7	114.8 (3)	C13—C14—H14	119.5
C5—N4—C9	110.4 (3)	C15—C14—H14	119.5
C5—N4—C21	110.0 (3)	C10—C15—C14	119.8 (4)
C9—N4—C21	110.6 (3)	C10—C15—H15	120.1
N2—C1—C2	110.4 (3)	C14—C15—H15	120.1
N2—C1—C16	120.6 (3)	C1—C16—H16A	109.5
C2—C1—C16	129.0 (3)	C1—C16—H16B	109.5
C3—C2—C4	117.5 (3)	H16A—C16—H16B	109.5
C3—C2—C1	105.4 (3)	C1—C16—H16C	109.5
C4—C2—C1	137.1 (3)	H16A—C16—H16C	109.5
N3—C3—N1	126.3 (3)	H16B—C16—H16C	109.5
N3—C3—C2	127.1 (3)	C18—C17—C4	128.8 (3)
N1—C3—C2	106.6 (3)	C18—C17—S2	111.7 (2)
C6—C4—C2	117.1 (3)	C4—C17—S2	119.5 (3)
C6—C4—C17	122.2 (3)	C17—C18—C19	108.0 (3)
C2—C4—C17	120.6 (3)	C17—C18—H18	126.0
N4—C5—C6	111.5 (3)	C19—C18—H18	126.0
N4—C5—H5A	109.3	C20—C19—C18	115.7 (4)
C6—C5—H5A	109.3	C20—C19—H19	122.2
N4—C5—H5B	109.3	C18—C19—H19	122.2
C6—C5—H5B	109.3	C19—C20—S2	112.1 (3)
H5A—C5—H5B	108.0	C19—C20—H20	124.0
C4—C6—C7	119.5 (3)	S2—C20—H20	124.0
C4—C6—C5	120.5 (3)	N4—C21—H21A	109.5
C7—C6—C5	120.0 (3)	N4—C21—H21B	109.5
N3—C7—C6	124.0 (3)	H21A—C21—H21B	109.5
N3—C7—C8	116.7 (3)	N4—C21—H21C	109.5
C6—C7—C8	119.3 (3)	H21A—C21—H21C	109.5
C22—C8—C7	119.9 (3)	H21B—C21—H21C	109.5
C22—C8—C9	124.1 (3)	C8—C22—C23	131.3 (3)
C7—C8—C9	115.9 (3)	C8—C22—H22	114.4
N4—C9—C8	112.0 (3)	C23—C22—H22	114.4
N4—C9—H9A	109.2	C24—C23—C22	123.9 (3)
C8—C9—H9A	109.2	C24—C23—S1	109.9 (2)
N4—C9—H9B	109.2	C22—C23—S1	126.2 (3)
C8—C9—H9B	109.2	C23—C24—C25	110.4 (3)
H9A—C9—H9B	107.9	C23—C24—H24	124.8
C15—C10—C11	119.6 (3)	C25—C24—H24	124.8
C15—C10—N1	120.7 (3)	C26—C25—C24	114.0 (4)
C11—C10—N1	119.7 (3)	C26—C25—H25	123.0
C12—C11—C10	119.4 (4)	C24—C25—H25	123.0
C12—C11—H11	120.3	C25—C26—S1	112.5 (3)
C10—C11—H11	120.3	C25—C26—H26	123.7
C13—C12—C11	121.3 (4)	S1—C26—H26	123.7

C3—N1—N2—C1	0.9 (4)	C6—C7—C8—C9	4.5 (5)
C10—N1—N2—C1	−178.9 (3)	C5—N4—C9—C8	62.2 (4)
N1—N2—C1—C2	−0.7 (4)	C21—N4—C9—C8	−175.8 (3)
N1—N2—C1—C16	179.8 (3)	C22—C8—C9—N4	143.5 (3)
N2—C1—C2—C3	0.3 (4)	C7—C8—C9—N4	−34.4 (4)
C16—C1—C2—C3	179.7 (3)	C3—N1—C10—C15	−24.3 (6)
N2—C1—C2—C4	178.8 (4)	N2—N1—C10—C15	155.4 (3)
C16—C1—C2—C4	−1.8 (7)	C3—N1—C10—C11	156.4 (3)
C7—N3—C3—N1	179.3 (3)	N2—N1—C10—C11	−23.9 (5)
C7—N3—C3—C2	−1.6 (5)	C15—C10—C11—C12	0.5 (6)
N2—N1—C3—N3	178.5 (3)	N1—C10—C11—C12	179.8 (3)
C10—N1—C3—N3	−1.8 (6)	C10—C11—C12—C13	−0.1 (6)
N2—N1—C3—C2	−0.7 (4)	C11—C12—C13—C14	−0.5 (6)
C10—N1—C3—C2	179.0 (3)	C12—C13—C14—C15	0.8 (6)
C4—C2—C3—N3	2.2 (5)	C11—C10—C15—C14	−0.2 (6)
C1—C2—C3—N3	−178.9 (3)	N1—C10—C15—C14	−179.5 (3)
C4—C2—C3—N1	−178.6 (3)	C13—C14—C15—C10	−0.4 (6)
C1—C2—C3—N1	0.3 (4)	C6—C4—C17—C18	−90.7 (4)
C3—C2—C4—C6	−1.7 (5)	C2—C4—C17—C18	91.2 (4)
C1—C2—C4—C6	180.0 (4)	C6—C4—C17—S2	92.1 (4)
C3—C2—C4—C17	176.6 (3)	C2—C4—C17—S2	−86.1 (4)
C1—C2—C4—C17	−1.8 (6)	C20—S2—C17—C18	−2.6 (3)
C9—N4—C5—C6	−58.1 (4)	C20—S2—C17—C4	175.1 (3)
C21—N4—C5—C6	179.6 (3)	C4—C17—C18—C19	−174.7 (3)
C2—C4—C6—C7	0.8 (5)	S2—C17—C18—C19	2.8 (4)
C17—C4—C6—C7	−177.4 (3)	C17—C18—C19—C20	−1.6 (5)
C2—C4—C6—C5	−180.0 (3)	C18—C19—C20—S2	−0.4 (5)
C17—C4—C6—C5	1.8 (5)	C17—S2—C20—C19	1.7 (3)
N4—C5—C6—C4	−151.4 (3)	C7—C8—C22—C23	179.2 (3)
N4—C5—C6—C7	27.8 (4)	C9—C8—C22—C23	1.3 (6)
C3—N3—C7—C6	0.6 (5)	C8—C22—C23—C24	−166.9 (4)
C3—N3—C7—C8	−177.7 (3)	C8—C22—C23—S1	12.1 (6)
C4—C6—C7—N3	−0.3 (5)	C26—S1—C23—C24	1.5 (3)
C5—C6—C7—N3	−179.5 (3)	C26—S1—C23—C22	−177.6 (3)
C4—C6—C7—C8	177.9 (3)	C22—C23—C24—C25	177.2 (3)
C5—C6—C7—C8	−1.3 (5)	S1—C23—C24—C25	−1.9 (3)
N3—C7—C8—C22	4.8 (5)	C23—C24—C25—C26	1.4 (4)
C6—C7—C8—C22	−173.6 (3)	C24—C25—C26—S1	−0.2 (5)
N3—C7—C8—C9	−177.2 (3)	C23—S1—C26—C25	−0.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C26—H26···N2ⁱ	0.93	2.57	3.445 (3)	157
C20—H20···Cg6ⁱⁱ	0.93	2.93	3.680 (3)	139

Symmetry codes: (i) x+1, y+1, z; (ii) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formula	C₂₆H₂₂N₄S₂
M_r	454.60
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	10.7187 (16), 10.9704 (19), 11.153 (2)
α, β, γ (°)	109.785 (2), 102.364 (1), 104.201 (1)
V (Å³)	1131.0 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.18 × 0.17 × 0.16

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.955, 0.960
No. of measured, independent and observed [I > 2σ(I)] reflections	5846, 3918, 2322
R_int	0.025
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.176, 1.00
No. of reflections	3918
No. of parameters	291
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.31, −0.43

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C26—H26···N2ⁱ	0.93	2.57	3.445 (3)	157
C20—H20···Cg6ⁱⁱ	0.93	2.93	3.680 (3)	139

Symmetry codes: (i) x+1, y+1, z; (ii) x+1, y+1, z+1.

Acknowledgements

The authors thank the National Natural Science Foundation of China (grant No. 20672090), the Natural Science Foundation of Jiangsu Province (grant No. BK2006033) and the Six Kinds of Professional Elite Foundation of Jiangsu Province (grant No. 06-A-039) for financial support.

References

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Volume 65| Part 5| May 2009| Pages o1109-o1110

doi:10.1107/S1600536809014810

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

3,6-Di­methyl-1-phenyl-4-(2-thien­yl)-8-(2-thienylmethyl­ene)-5,6,7,8-tetra­hydro-1H-pyrazolo[3,4-b][1,6]naphthyridine

Related literature

Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

organic compounds

3,6-Dimethyl-1-phenyl-4-(2-thienyl)-8-(2-thienylmethylene)-5,6,7,8-tetrahydro-1H-pyrazolo[3,4-b][1,6]naphthyridine